EP0993481B1 - Procede de production de polycarbonates ramifies - Google Patents

Procede de production de polycarbonates ramifies Download PDF

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Publication number
EP0993481B1
EP0993481B1 EP98937493A EP98937493A EP0993481B1 EP 0993481 B1 EP0993481 B1 EP 0993481B1 EP 98937493 A EP98937493 A EP 98937493A EP 98937493 A EP98937493 A EP 98937493A EP 0993481 B1 EP0993481 B1 EP 0993481B1
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EP
European Patent Office
Prior art keywords
bis
hydroxyphenyl
mol
mbar
dimethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98937493A
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German (de)
English (en)
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EP0993481A1 (fr
Inventor
Annett KÖNIG
Lothar Bunzel
Uwe Hucks
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
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Bayer MaterialScience AG
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Publication of EP0993481A1 publication Critical patent/EP0993481A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
    • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
    • C08G64/1616—Aliphatic-aromatic or araliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates

Definitions

  • the present invention is a process for the preparation of branched polycarbonates by the melt transesterification of diphenols, diaryl carbonates and branching optionally using catalysts at temperatures between 80 and 400 ° C and at pressures between 1013.5 mbar (1 atm.) And 0, 01 mbar, which is characterized in that as branching three to six-valent aliphatic alcohols selected from pentaerythritol or its self-condensation resulting ether dipentaerythritol glycerol, 1,2,3,6-hexantetrol and 2,5-dimethyl-1,2, 6-hexanetriol in amounts of 0.05 mol to 2 mol, preferably from 0.10 mol to 1.5 mol per 100 mol of diphenol.
  • the polycarbonates prepared by the process according to the invention are solvent-free and have a light inherent color, they preferably have a low OH end group content of ⁇ 1200 ppm and are characterized by increased melt stability and intrinsic viscosity and by a reduced dripping behavior in case of fire over linear polycarbonate.
  • EP-A 0 140 341 describes the preparation of a branched polycarbonate via the melt transesterification process using triaryl esters of tricarboxylic acids, for example trimellitic acid, as branching agent.
  • triaryl esters of tricarboxylic acids for example trimellitic acid
  • branching agent for example trimellitic acid
  • compound (II) is likely to undergo melt-esterification temperatures with elimination of transform and decompose.
  • the aliphatic alcohols of the formula (I) to be used according to the invention are thermally stable, ie do not degrade, but are at most synthesized to higher molecular weight ethers.
  • the process or melt transesterification according to the invention offers a practical method of preparing aliphatic branching sites with good reproducibility into thermoplastic, aromatic Polycarbonate to install.
  • hydroquinone examples which may be mentioned are hydroquinone, resorcinol, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, ethers, sulfoxides, sulfones, and ⁇ , ⁇ -bis (hydroxyphenyl) - diisopropylbenzenes, as well as their nuclear alkylated and nucleated compounds called.
  • Suitable diphenols are for example in the U.S. Patents 3,028,365 . 2,999,835 . 3 062 781 . 3 148 172 and 4 982 014 , in the German Offenlegungsschriften 1 570 703 and 2 063 050 , as well as in the monograph " H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964 "described.
  • Preferred diphenols are 4,4'-dihydroxyphenyl, 2,2-bis (4-hydroxyphenyl) -propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, ⁇ , ⁇ -bis (4-hydroxyphenyl) -p-diisopropylbenzene, ⁇ , ⁇ -bis (4-hydroxyphenyl) -m-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, Bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl)
  • diphenols are, for example 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane, 9,9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene.
  • Carbonic acid esters in the context of the present invention are di-C 6 -C 14 -aryl esters, preferably the diesters of phenol or alkyl-substituted phenols, ie diphenyl carbonate or dicresyl carbonate.
  • the carbonic acid diesters are used in 1.01 to 1.30 mol, preferably in 1.02 to 1.15 mol.
  • the diphenols, carbonic acid diesters and branching agents are used in as pure a form as possible. Pure diphenols and pure carbonic acid esters are obtained by recrystallization in a known manner. Laundry or distillation and other ways to clean the diphenols and carbonates.
  • Preferred catalysts to be used are the ammonium and phosphonium salts known from the literature (see, for example US-A 3 442 864 . JP-A-14742/72 . US Pat. No. 5,399,659 and DE-A 19 539 290 ).
  • R 1 to R 4 independently of one another can be C 1 -C 16 -alkyls / aryls or cycloalkyls and X - is an anion in which the corresponding acid-base pair H + + X - ⁇ HX has a pK B of ⁇ 11 ,
  • Suitable ammonium salts or phosphonium salts are, for example Tetramethylammoniumtetraphenylboranat, tetraphenyl Tetraphenylphosphoniumfluorid, Tetraphenylphosphoniumtetraphenylboranat, Dimethyldiphenylammoniumhydroxid, tetraethylammonium, tetramethylammonium, Tetramethylammonium acetate and Tetramethylammonium fluoride.
  • Preferred catalysts to be used are also guanidines according to US Pat. No. 5,319,066 , Also suitable are imidazoles.
  • the catalysts are preferably used in amounts of 10 -8 to 10 -4 mol, more preferably in a concentration of 10 -7 to 10 -5 mol, based on 1 mol of diphenol.
  • the catalysts may be used alone or in combination with each other; they may be added at the beginning of the process or only during the course of the process.
  • the process according to the invention can generally be carried out in one stage, in which case all reactants are at temperatures from 80 ° C. to 250 ° C., preferably from 100 to 230 ° C. and in particular from 120 to 190 ° C. under normal pressure in 0.1 to 5 Hours, preferably in 0.25 to 3 hours to be melted.
  • branching agents to be used according to the invention can also be added only a little later to the melt of diphenols and diaryl carbonates.
  • an oligocarbonate is prepared by applying a vacuum and raising the temperature by distilling off the monophenol.
  • the polycarbonate is then produced in the polycondensation by further increasing the temperature to 240 to 400 ° C and lowering the pressure to 0.01 mbar.
  • reaction according to the invention without the use of catalysts requires very long reaction times, which is why the reaction is preferably carried out using one or two catalysts.
  • this is added either before the melting or the melt before oligocarbon production.
  • these are preferably added separately, one at the beginning of the reactant and the second of the melt of the oligocarbonate.
  • reaction times can be shortened and the reaction temperatures can be reduced, especially in the polycondensation phase.
  • the temporally separate addition of two catalysts is generally associated with the stepwise process, that is, that the reaction is interrupted to at least one point. This is preferably done after reaching the oligocarbonate stage.
  • alkali metal or alkaline earth metal catalysts in amounts of 10 -8 to 10 -4 mol, preferably from 10 -7 to 10 -5 mol, per mole of diphenol originally used used.
  • alkali metal or alkaline earth metal catalysts in amounts of 10 -8 to 10 -4 mol, preferably from 10 -7 to 10 -5 mol, per mole of diphenol originally used used.
  • examples are the lithium, sodium, potassium, cesium, calcium, barium, magnesium, hydroxides, carbonates, halides, phenolates, diphenolates, fluorides, acetates, phosphates, hydrogen phosphates and boronate.
  • the stepwise process control also offers the possibility to use the branch later, so for example, only the oligocarbonate.
  • branching agents to be used according to the invention can be added in bulk, solid or melted, as a solution in water, melted in phenol or as a concentrate in the oligo- or polycarbonate in question.
  • phenols such as camylphenol or 4-phenylphenol in amounts of 0.01 to 10 mol%, can be used selectively per mole of diphenol.
  • the temperature control in the two-stage procedure is for the preparation of oligocarbonates between 100 and 290 ° C, preferably between 150 and 280 ° C and for the polycondensation of the oligocarbonates between 230 ° C and 400 ° C, preferably between 250 and 320 ° C.
  • the pressure range for the preparation of the oligocarbonates is between 1 bar and 0.5 mbar, preferably between 500 mbar and 1 mbar.
  • the pressure range is between 100 mbar and 0.01 mbar.
  • the oligocarbonates have average molecular weights M W of 3000 to 24000, preferably 5000 to 20,000, determined by measuring the relative solution viscosity in dichloromethane or in mixtures of equal amounts by weight phenol / o-dichlorobenzene calibrated by light scattering.
  • the polycarbonates obtainable by the process according to the invention have average weight molecular weights of 12,000 to 60,000, preferably 15,000 to 40,000, determined by measuring the relative solution viscosity in dichloromethane or mixtures of equal amounts by weight phenol / o-dichlorobenzene, calibrated by light scattering.
  • the process according to the invention can be carried out continuously or batchwise, for example in stirred kettles, thin-film evaporators, falling-film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors and high-viscosity disk reactors.
  • stabilizers eg, UV, thermal, gamma ray stabilizers
  • antistatic agents eg, UV, thermal, gamma ray stabilizers
  • flow aids e.g., IR, thermal, gamma ray stabilizers
  • Mold release agents e.g., fire retardants, pigments, finely divided minerals, fibrous materials, eg alkyl and aryl phosphites, phosphates, phosphanes, low molecular weight carboxylic acid esters, halogen compounds, salts, chalk, quartz powder, glass and carbon fibers.
  • polystyrene may also be added to the polycarbonates according to the invention, e.g. Polyolefins, polyurethanes, polystyrene.
  • the polycarbonates prepared by the novel processes are suitable both for extrusion and for injection molding. Because of the excellent stability of the melt strand, they are also suitable for the production of hollow bodies by the blow molding process.
  • the excellent pseudoplastic properties make it possible, for example, to obtain easily accessible extrusion films with good mechanical properties and reduced stress corrosion cracking.
  • SV number For characterizing the branching of polycarbonates it can be used SV number. It is defined as the quotient of the melt viscosities at 10 s -1 and 10 3 s -1 . The larger this quotient, the greater the deviation from the Newtonian behavior, ie the greater the intrinsic viscosity.
  • Example 1 As Example 1, with only 0.004 mol (0.272 g) of pentaerythritol.
  • Example 1 As Example 1, with only 0.008 mol (0.544 g) of pentaerythritol.
  • Example 1 As Example 1, with only 0.003 moles (0.381 g) of dipentaerythritol.
  • Example 1 with only 0.008 mol (1.016 g) of dipentaerythritol.
  • Color number See 1 - - 380 1,246 1,232 1.80 0.28 1 pentaerythritol 0.3 260 1,328 1,319 2.55 0.30 2 pentaerythritol 0.4 380 1,335 1,330 3.27 0.30 3 pentaerythritol 0.8 360 1,396 1,378 5.32 0.32 4 dipentaerythritol 0.3 300 1,317 1,299 2.58 0.35 5 dipentaerythritol 0.8 320 1,398 1,381 3.97 0.31 * measured in dichloromethane at 25 ° C and 5 g / l.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (2)

  1. Procédé pour la préparation de polycarbonates ramifiés selon le procédé de transestérification à l'état de fusion de diphénols, de carbonates de diaryle et d'agents de ramification, éventuellement en utilisant des catalyseurs à des températures comprises entre 80°C et 400°C et à des pressions comprises entre 1013,5 mbar (1 Atm) et 0,01 mbar, caractérisé en ce que l'on utilise comme agents de ramification des alcools aliphatiques tri- à hexavalents choisis parmi le pentaérythritol ou son éther-dipentaérythritol produit par autocondensation, la glycérine, le 1,2,3,6-hexanetétrol et le 2,5-diméthyl-1,2,6-hexanetriol dans des quantités de 0,05 mol à 2 mol pour 100 mol de diphénol.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise les agents de ramification dans des quantités de 0,1 mol à 1,5 mol pour 100 mol de diphénol.
EP98937493A 1997-06-30 1998-06-17 Procede de production de polycarbonates ramifies Expired - Lifetime EP0993481B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19727709A DE19727709A1 (de) 1997-06-30 1997-06-30 Verfahren zur Herstellung von verzweigten Polycarbonaten
DE19727709 1997-06-30
PCT/EP1998/003653 WO1999001495A1 (fr) 1997-06-30 1998-06-17 Procede de production de polycarbonates ramifies

Publications (2)

Publication Number Publication Date
EP0993481A1 EP0993481A1 (fr) 2000-04-19
EP0993481B1 true EP0993481B1 (fr) 2008-03-05

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EP98937493A Expired - Lifetime EP0993481B1 (fr) 1997-06-30 1998-06-17 Procede de production de polycarbonates ramifies

Country Status (10)

Country Link
US (1) US6307006B1 (fr)
EP (1) EP0993481B1 (fr)
JP (1) JP4302781B2 (fr)
CN (1) CN1141329C (fr)
AU (1) AU8627098A (fr)
BR (1) BR9810953A (fr)
DE (2) DE19727709A1 (fr)
ES (1) ES2301206T3 (fr)
TW (1) TW491867B (fr)
WO (1) WO1999001495A1 (fr)

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CN1250605C (zh) * 2001-03-26 2006-04-12 拜尔公司 具有显著剪切变稀行为的聚碳酸酯
US6437083B1 (en) 2001-12-06 2002-08-20 General Electric Company Process for preparing branched aromatic polycarbonates
US6504002B1 (en) 2001-12-21 2003-01-07 General Electric Company Process for the production of branched melt polycarbonate by late addition of fries-inducing catalyst
US6747119B2 (en) 2002-03-28 2004-06-08 General Electric Company Method and system for preparing a polycarbonate, copolymerization reagent and polycarbonate
US7342059B2 (en) * 2003-01-13 2008-03-11 Eastman Chemical Company Polyester-polycarbonate blends useful for extrusion blow-molding
JP4413226B2 (ja) * 2003-09-12 2010-02-10 ビーエーエスエフ ソシエタス・ヨーロピア 高分岐型または超分岐型の高官能性ポリカルボナート、その製造方法および使用方法
US7345104B2 (en) * 2003-12-16 2008-03-18 Eastman Chemical Company Polyester-polycarbonate blends useful for extrusion blow-molding
US7297736B2 (en) 2004-10-28 2007-11-20 Eastman Chemical Company Neopentyl glycol containing polyesters blended with polycarbonates
US20060287479A1 (en) 2005-06-17 2006-12-21 Crawford Emmett D Polyester compositions containing cyclobutanediol and articles made therefrom
US7704605B2 (en) 2006-03-28 2010-04-27 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7226985B2 (en) 2005-07-12 2007-06-05 Eastman Chemical Company Polyester-polycarbonate compositions
US7230065B2 (en) 2005-07-12 2007-06-12 Eastman Chemical Company Blends of polycarbonate and sulfone copolyesters
US7425590B2 (en) 2005-07-12 2008-09-16 Eastman Chemical Company Transparent two phase polyester-polycarbonate compositions
EP2156935A3 (fr) * 2005-10-28 2010-07-28 Eastman Chemical Company Accessoires de restaurant comprenant des compositions de polyester formées de 2,2,4,4-tétramethyl-1,3-cyclobutanédiol et de 1,4-cyclohexanediméthanol
US8193302B2 (en) 2005-10-28 2012-06-05 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof
CA2625846A1 (fr) 2005-10-28 2007-05-10 Eastman Chemical Company Compositions de polyester comprenant du cyclobutanediol et au moins un compose phosphoreux
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US7737246B2 (en) 2005-12-15 2010-06-15 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor
US9169388B2 (en) 2006-03-28 2015-10-27 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US7759456B2 (en) * 2006-06-30 2010-07-20 Sabic Innovative Plastics Ip B.V. Branched polycarbonate resins and processes to prepare the same
US20080103235A1 (en) * 2006-11-01 2008-05-01 Wesley Raymond Hale Clear blends of bisphenol a polycarbonate and copolyesters
US20080118729A1 (en) * 2006-11-16 2008-05-22 General Electric Company Thermoplastic composition, method of making, and articles formed therefrom
CA2705870A1 (fr) 2007-11-21 2009-06-04 Eastman Chemical Company Biberons en matiere plastique, autres articles moules par extrusion-soufflage et leurs procedes de fabrication
US8501287B2 (en) 2007-11-21 2013-08-06 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US20090186966A1 (en) * 2008-01-22 2009-07-23 Sabic Innovative Plastics Ip B.V. Thermoplastic polyestercarbonate composition
US8198371B2 (en) 2008-06-27 2012-06-12 Eastman Chemical Company Blends of polyesters and ABS copolymers
US8895654B2 (en) 2008-12-18 2014-11-25 Eastman Chemical Company Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid
EP2374829A1 (fr) * 2010-04-07 2011-10-12 Bayer MaterialScience AG Polycarbonate en fusion ramifié doté d'un taux moindre de structures erronées
CN102958976B (zh) * 2010-07-08 2014-11-26 旭化成化学株式会社 支链聚碳酸酯的连续制造方法
US8420869B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8394997B2 (en) 2010-12-09 2013-03-12 Eastman Chemical Company Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8420868B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US20130217830A1 (en) 2012-02-16 2013-08-22 Eastman Chemical Company Clear Semi-Crystalline Articles with Improved Heat Resistance
KR20140075516A (ko) * 2012-12-11 2014-06-19 제일모직주식회사 고분지형 폴리카보네이트 수지 및 그 제조방법
US10017640B2 (en) 2013-03-08 2018-07-10 Covestro Llc Halogen free flame retarded polycarbonate
CN106560483B (zh) * 2016-05-19 2017-11-17 福建盈科百创电子有限公司 一种安防用聚碳酸酯树脂材料及其生产工艺

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EP0708130A1 (fr) * 1994-10-20 1996-04-24 General Electric Company Production de polycarbonates ramifiés par un procédé d'équilibrage

Also Published As

Publication number Publication date
AU8627098A (en) 1999-01-25
DE19727709A1 (de) 1999-01-07
ES2301206T3 (es) 2008-06-16
HK1029358A1 (en) 2001-03-30
CN1141329C (zh) 2004-03-10
WO1999001495A1 (fr) 1999-01-14
DE59814185D1 (de) 2008-04-17
US6307006B1 (en) 2001-10-23
JP2002508801A (ja) 2002-03-19
BR9810953A (pt) 2000-09-26
JP4302781B2 (ja) 2009-07-29
CN1261902A (zh) 2000-08-02
TW491867B (en) 2002-06-21
EP0993481A1 (fr) 2000-04-19

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